(1S,7R,8S)-8-acetyl-1,4-dimethylbicyclo[5.3.0]dec-3-ene | 461663-45-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,7R,8S)-8-acetyl-1,4-dimethylbicyclo[5.3.0]dec-3-ene
• 英文别名: 1-[(1S,3aS,8aR)-3a,6-dimethyl-2,3,4,7,8,8a-hexahydro-1H-azulen-1-yl]ethanone
• CAS: 461663-45-6
• 化学式: C₁₄H₂₂O
• 分子量: 206.328
• InChiKey: NTTHZFWZFMNEMX-MGPQQGTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,7R,8S)-8-acetyl-1,4-dimethylbicyclo[5.3.0]dec-3-ene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以51%的产率得到(1S,3R,4S,7R,8S)-8-acetyl-3,4-epoxy-1,4-dimethylbicyclo[5.3.0]decane
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Liverwort Diterpenes, (−)-13(15)E,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene and (−)-13(15)Z,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene, by Use of the Ring Closing Metathesis Reaction Applied to Seven-Membered Carbocycles with a Trisubstituted Double Bond

  摘要：

  Seven-membered cyclic compounds possessing trisubstituted double bonds have been effectively constructed employing the Grubbs catalyst to effect olefin metathesis. The keto ester does not undergo cyclization; however, alcohols protected by the silyl groups smoothly cyclized into seven-membered compounds. The product was successfully converted to (-)-13(15)E,16E-3P,4P-epoxy18-hydroxysphenoloba-13(15),16-diene and (-)-13(15)Z,16E-3beta,4beta-epoxy-18-hydroxysphenoloba-13(15),16-diene, liverwort diterpenes isolated from Anastrophyllum auritum to establish the absolute configuration.

  DOI：

  10.1021/jo020287d
• 作为产物：
  描述：

  3-[(1S)-1,4-dimethyl-7-triethylsilyloxycyclohept-3-en-1-yl]propyl 4-methylbenzenesulfonate 在 吡啶 、 氯化亚砜 、 jones reagent 、 18-冠醚-6 、 potassium tert-butylate 、 potassium carbonate 、 magnesium 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 丙酮 为溶剂， 反应 29.0h， 生成 (1S,7R,8S)-8-acetyl-1,4-dimethylbicyclo[5.3.0]dec-3-ene
  参考文献：
  名称：

  Total Synthesis and Absolute Configuration of Liverwort Diterpenes, (−)-13(15)E,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene and (−)-13(15)Z,16E-3β,4β-Epoxy-18-hydroxysphenoloba-13(15),16-diene, by Use of the Ring Closing Metathesis Reaction Applied to Seven-Membered Carbocycles with a Trisubstituted Double Bond

  摘要：

  Seven-membered cyclic compounds possessing trisubstituted double bonds have been effectively constructed employing the Grubbs catalyst to effect olefin metathesis. The keto ester does not undergo cyclization; however, alcohols protected by the silyl groups smoothly cyclized into seven-membered compounds. The product was successfully converted to (-)-13(15)E,16E-3P,4P-epoxy18-hydroxysphenoloba-13(15),16-diene and (-)-13(15)Z,16E-3beta,4beta-epoxy-18-hydroxysphenoloba-13(15),16-diene, liverwort diterpenes isolated from Anastrophyllum auritum to establish the absolute configuration.

  DOI：

  10.1021/jo020287d

文献信息

• Preparation of Seven-Membered Carbocycles Using Ring-Closing Metathesis Reaction and Application to Syntheses of Tormesol and Cyathane Skeleton
  作者：Katsuyuki Nakashima、Norihiro Fujisaki、Kosuke Inoue、Atsushi Minami、Chisako Nagaya、Masakazu Sono、Motoo Tori

  DOI：10.1246/bcsj.79.1955

  日期：2006.12

  Various precursors were synthesized and were reacted with the Grubbs reagent as well as the second generation Grubbs reagent to cyclize them into seven-membered carbocycles with di- or tri-substituted double bonds. These reactions were used to synthesize (−)-tormesol, which is an enantiomer of sphenolobane-type diterpene that was isolated from Halimium viscosum, and a basic skeleton of cyathane-type diterpene.

  我们合成了各种前体，并用格拉布斯试剂和第二代格拉布斯试剂将它们环化成具有二或三取代双键的七元碳环。利用这些反应合成了 (-)-tormesol （一种从 Halimium viscosum 分离出来的 sphenolobane 型二萜的对映体）和一种 cyathane 型二萜的基本骨架。
• Approach to the Synthesis of Diterpenes with the Bicyclo[5.3.0]decane System: (±) 10-epi-tormesol
  作者：Isidro S. Marcos、Isabel M. Oliva、David Díez、Pilar Basabe、Anna M. Lithgow、Rosalina F. Moro、Narciso M. Garrido、Julio G. Urones

  DOI：10.1016/0040-4020(95)00796-b

  日期：1995.11

  The synthesis of (±) 10-epi-tormesol, 27, has been achieved from (±) 1-acetyl-3a,6 dimethylhexahydroazulene 1, by coupling of 5, a dehydroderivative of 1, with 23. The same synthetic procedure afforded a series of diterpenes 24–26 and 28 with the same biannular system. Direct reduction of 1 with different methods does not give the desired spatial relationship (trans/cis) between Me-C7/H-6/H-10 on the

  的合成（±）-10-外延-tormesol，27，已经从实现（±）1-乙酰基3a中，6 dimethylhexahydroazulene 1，通过连接5，一个dehydroderivative的1，与23。相同的合成程序提供了具有相同双环系统的一系列二萜24-26和28。用不同方法直接还原1不会在底物上的Me-C 7 / H-6 / H-10之间产生所需的空间关系（反式/顺式），而是提供反式/反式（化合物5和18）和顺式/顺式（化合物9）。间接还原：环氧化反应，然后进行催化氢化，在中间体上提供了所需的立体化学，但脱氧导致C-10发生差向异构化。这一综合成就证实了几年前分配给tormesol的原始结构。